Method for breaking petroleum emulsions and the like using micellar solutions of thin film spreading agents comprising an acylated polyether polyol

ABSTRACT

The invention relates to the use of a homogeneous, micellar solution of a water-insoluble thin film spreading agent for the breaking of petroleum emulsions, and the like, comprising: (a) from between about 5% and about 75% by weight of an acylated polyether polyol; (b) from between about 2% and about 30% by weight of a hydrotropic agent; (c) from between about 2% and about 30% by weight of an amphipathic agent; and (d) from between about 15% and about 90% by weight of water.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to the use of a micellar solution of a thin filmspreading agent comprising an acylated polyether polyol in the breakingor prevention of petroleum emulsions. More specifically, the inventionrelates to a composition in which water replaces all or a substantialpart of the organic solvents formerly required for preparation of liquidsolutions of this interfacially active compound.

2. Description of the Prior Art

One of the principal uses of the present composition is in the breakingof petroleum emulsions to permit the separation thereof into two bulkphases. Much of the crude petroleum oil produced throughout the world isaccompanied by some water or brine which originates in or adjacent tothe geological formation from which the oil is produced. The amount ofaqueous phase accompanying the oil may vary from a trace to a very largepercentage of the total fluid produced. Due to the natural occurrence inmost petroleum of oil-soluble or dispersible emulsifying agents, much ofthe aqueous phase produced with oil is emulsified therein, formingstable water-in-oil emulsions.

The literature contains numerous references to such emulsions, theproblems resulting from their occurrence, and the methods employed tobreak them and separate salable petroleum. See, for example, "TheTechnology of Resolving Petroleum Emulsions" by L. T. Monson and R. W.Stenzel, p. 535 et seq in Colloid Chemistry Vol VI, Ed. by JeromeAlexander, Rheinhold Publishing Corp., New York (1946) and "InterfacialFilms Affecting the Stability of Petroleum Emulsions" by Chas. M. Blair,Jr. in Chemistry and Industry (London), p. 538 et seq (1960).

Early demulsifiers used to resolve petroleum emulsions werewater-soluble soaps, Twitchell reagents, and sulfonated glycerides.These products were readily compounded with water to form easilypumpable liquids and were conveniently applied by pumping into flowlines at the well head or by washing down the casing annulus with waterto commingle with well fluids prior to their flow to the surface. Theseproducts, however, were effective only at relatively high concentrationsand their use added substantially to the cost of production.

Some time ago, it was discovered that certain lightly sulfonated oils,acetylated castor oils and various polyesters, all of which wereinsoluble in water but soluble in alcohols and aromatic hydrocarbons,were much more effective in breaking emulsions. Accordingly, essentiallyall commercial demulsifier development has led to production of agentswhich are insoluble in both water and petroleum oils and have otherproperties to be described below which cause them to spread at oil-waterinterfaces to form very thin, mobile films which displace anyemulsifying agent present in the oil to allow coalescence of dispersedwater droplets. Generally, such interfacially active compounds arehereafter referred to as Thin Film Spreading Agents, or "TFSA's". In thepast, these have had to be compounded with and dissolved in alcohols orhighly aromatic hydrocarbon solvents in order to produce readily appliedliquid compositions. A wide variety of such compositions are required totreat the many different emulsions encountered throughout the world.

While present TFSA compositions are highly effective, being, perhaps, upto fifty to a hundred times more effective per unit volume than theoriginal water-soluble demulsifiers, they suffer serious practicaldeficiencies because of their solubility characteristics. For example,alcohols and the aromatic hydrocarbons, which are required forpreparation of liquid, pumpable compositions, are quite expensive, todayapproaching in cost that of the active demulsifier ingredient itself.Further, such solvents are flammable and thus create safety problems andentail more expense in shipping, storing and use. The low flash pointflammability can be improved by using high boiling aromatic solvents,but these are increasingly rare, expensive and dangerous from thestandpoint of carcinogenicity and dermatological effects.

Still further, present demulsifiers cannot generally be used in asubterranean oil or gas well, injection well, or the like, since theycannot be washed down with either water (or brine) or a portion of theproduced oil, and, being viscous liquids which are required in verysmall amounts, they cannot be reliably and continuously deliveredseveral thousand feet down at the fluid level in a typical well withoutuse of elaborate and expensive delivery means.

Other applications of TFSA compositions would be facilitated if theywere readily soluble or dispersible in water. For example, much heavy,viscous oil is produced in the United States by steam injectionprocedures. Typically, wet steam is injected into the oil producingstrata for several weeks in order to heat the oil, lower its viscosityand increase reservoir energy. Steam injection is then stopped and oilis flowed or pumped from the bore hole which was used for steaminjection. Much of the water resulting from condensation of the steam isalso produced with the oil in emulsified form. Since emulsions are moreviscous than the external phase at the same temperature, and thus createincreased resistance to flow, productivity of the steamed wells can beimproved by injecting a water-soluble demulsifier into the wet steamduring the steam injection period to prevent emulsion formation. See,for example, U.S. Pat. No. 3,396,792, dated Apr. 1, 1966, to F. D.Muggee. At present, the requirement of water solubility seriously limitsthe choice of demulsifiers for use in steam or water injection to therelatively inefficient compositions.

As disclosed in my co-pending applications, Ser. No. 045,479, filed June4, 1979 and entitled "Method Of Recovering Petroleum From A SubterraneanReservoir Incorporating A Polyether Polyol", Ser. No. 45,478, filed June4, 1979, now U.S. Pat. No. 4,260,019, and entitled "Method of RecoveringPetroleum From A Subterranean Reservoir Incorporating ResinousPolyalkylene Oxide Adducts", Ser. No. 45,360, filed June 4, 1979, nowU.S. Pat. No. 4,216,828, and entitled "Method Of Recovering PetroleumFrom A Subterranean Reservoir Incorporating An Acylated PolyetherPolyol", and Ser. No. 45,470, filed June 4, 1979, and entitled "Methodof Recovering Petroleum From A Subterranean Reservoir IncorporatingPolyepoxide Condensates Of Resinous Polyalkylene Oxide Adducts AndPolyether Polyols", TFSA's are useful in processes for enhanced recoveryof petroleum. Used in such processes involving displacement of residualoil by aqueous solutions, polymer solutions and other aqueous systems,these agents act to increase the amount of oil recovered. Such actionpossibly arises from their ability to further water wetting of reservoirrock, lessen the viscosity of the oil-water interfacial layer andpromote coalescence of dispersed droplets of either water or oil in theother phase.

By use of the present aqueous micellar solutions, the introduction ofTFSA into aqueous displacement or flooding fluids is greatlyfacilitated. In addition, the present micellar solutions, per se, or incombination with other components, can be used as the flooding agent oras a pretreating bank or slug ahead of other aqueous fluids.

Other applications for the present TFSA micellar solutions include theiruse as flocculation aids for finely ground hematite and magnetite oresduring the desliming step of ore beneficiation, as additives forimproving the oil removal and detergent action of cleaning compositionsand detergents designed for use on polar materials, for the improvementof solvent extraction processes such as those used in extraction ofantibiotic products from aqueous fermentation broths with organicsolvents, for the improvement of efficiency and phase separation in thepurification and concentration of metals by solvent extraction withorganic solutions of metal complex-forming agents, and as assistants toimprove the wetting and dying of natural and synthetic fibers and forother processes normally involving the interface between surfaces ofdiffering polarity or wetting characteristics.

SUMMARY OF THE INVENTION

A primary object of the present invention is to provide aqueous, liquidcompositions of these TFSA's having new and useful characteristics whichallow production of: petroleum emulsion breakers and emulsion preventingcompositions free or relatively free of highly flammable andenvironmentally objectionable aromatic hydrocarbons; compositions havinga comparatively low cost; compositions which are soluble or dispersiblein water and which, therefore, can often be applied by more effectivemethods than can existing products; compositions which can be used inenhanced recovery operations such as steam flooding and aqueous mediumflooding where present products cannot be readily applied; andcompositions which can be compounded with water-soluble reagents ofother types, such as corrosion inhibitors, wetting agents, scaleinhibitors, biocides, acids, etc., to provide multipurpose compounds foruse in solving many oil well completion, production, transportation andrefining problems.

In accordance with the present invention, these aims are accomplished bymeans of amphipathic agents which are capable of forming micellarsolutions and which by this mechanism or other undefined actions,combined with those of a second essential component which will bereferred to as a hydrotropic agent, are able to form homogeneous aqueoussolutions containing a relatively wide range of concentrations of TFSA.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The TFSA compositions of the present invention can be broadlycategorized by the following general characteristics:

1. Solubility in water and isooctane at about 25° C. is less than about1% by volume;

2. Solubility parameter at about 25° C. is in the range of from betweenabout 6.8 to about 8.5, with a majority in the range of from between 7.0and about 7.9; and

3. Spread at the interface between white, refined mineral oil anddistilled water to form films having a calculated thickness no greaterthan about 20 Angstroms at a spreading pressure of about 16 dynes percm.

TFSA compositions having these properties are generally organic polymersor semi-polymers having molecular weights ranging from about 2,000 toabout 100,000 and having structures containing a multiplicity ofdistributed hydrophilic and hydrophopic moieties arranged in linear orplanar arrays which make them surface active and lead to theiradsorption at oil-water interfaces to form very thin films.

Unlike most commonly encountered surface-active compounds, the presentTFSA appears to be incapable of forming a micelle in either oil orwater. The distributed and alternating occurrence of polar and nonpolaror hydrophilic and hydrophobic groups in the molecule apparentlyprevents the kind of organization required for micelle formation andthus impairs dispersion or solution in either water or low polarityorganic solvents.

The TFSA's useful in the present invention have the previously recitedproperties:

1. The solubility in water and in isooctane at about 25° C. is less thanabout 1% by volume

Solubility tests may be run by placing a 1 ml sample (or the weight ofsolid product calculated to have a volume of 1 ml) in a graduatedcylinder of the type which may be closed with a ground glass stopper.Thereafter place 99 ml of water in the cylinder, close, place in a 25°C. water bath until thermal equilibrium is reached, and remove from thebath and shake vigorously for one hour. Return the sample to the bathfor five minutes and then repeat the shaking procedure. Finally, returnthe sample to the bath and allow it to stand quietly for one hour. Thecylinder contents should be carefully examined and any cloudiness oropacity of the liquid phase or the appearance of any sediment orundissolved material in the cylinder noted, thus indicating that thesample satisfied the requirement for insolubility in water.

Isooctane solubility is determined similarly by substituting thishydrocarbon for the water used above.

2. The Solubility Parameter (S.P.) at about 25° C. is from between about6.9 and about 8.5, inclusive

Methods of determination of solubility parameter are disclosed in JoelH. Hildebrand, "The Solubility of Nonelectrolytes", Third Edition, pgs.425 et seq. However, a simplified procedure, sufficiently accurate forqualification of a useful TFSA composition may be utilized. Componentsof a give solubility parameter are generally insoluble in hydrocarbon(non-hydrogen-bonding) solvents having a lower solubility parameter thanthemselves. Therefore, the present composition should be insoluble in ahydrocarbon solvent of a solubility parameter of about 6.8. Since thesolubility parameter of mixtures of solvents is an additive function ofvolume percentage of components in the mixture, test solutions of thedesired solubility parameters may be easily prepared by blending, forexample, benzene (S.P. 9.15) and isooctane (S.P. 6.85) orperfluoro-n-heptane (S.P. 5.7).

A mixture of about 72 parts of benzene with about 28 parts of isooctanewill provide a solvent having a solubility parameter of about 8.5 atroom temperature (about 25° C.). Perfluoro-n-heptane has a solubilityparameter of about 5.7 at 25° C., so a mixture of 68 parts of thissolvent with 32 parts of benzene provides a solvent with a solubilityparameter of about 6.8, or isooctane of a solubility parameter 6.85 maybe used.

When 5 ml of the TFSA are mixed with 95 ml of an 8.5 solubilityparameter solvent at room temperature, a clear solution should result.When 5 ml of TFSA is mixed with a 6.85 solubility parameter solvent, acloudy mixture or one showing phase separation should result. Solventmixtures have a solubility parameter between about 7.0 and about 7.9 maybe prepared as described above and utilized in a similar test procedure.

In interpreting the solubility parameter and other tests, it should berecognized that the TFSA consists not of a single material or compoundbut a cogeneric mixture of products containing a range of products ofmolecular weights distributed around the average molecular weight andeven containing small amounts of the starting compounds employed in thesynthesis. As a result, in running solubility and solubility parametertests, very slight appearances of cloudiness or lack of absolute clarityshould not be interpreted as a pass or a failure to pass the criteria.The intent of the test is to ensure that the bulk of the cogenericmixture, i.e., 75% or more, meets the requirement. When the result is indoubt, the solubility tests may be run in centrifuge tubes allowingsubsequent rapid phase separation by centrifuging, after which theseparated nonsolvent phase can be removed, any solvent contained in itcan be evaporated, and the actual weight or volume of separated phasecan be determined.

3. The TFSA should spread at the interface between distilled water andrefined mineral oil to form films with thickness no greater than about20 Angstroms (0.0020 micrometer) at a spreading pressure of about 16dynes per cm (0.016 Newton per meter)

Suitable methods of determining film pressure are disclosed in N. K.Adam, "Physics and Chemistry of Surfaces", Third Edition, OxfordUniversity Press, London, 1941, pgs. 20 et seq, and C. M. Blair, Jr.,"Interfacial Films Affecting The Stability of Petroleum Emulsions",Chemistry and Industry (London), 1960, pgs. 538 et seq. Film thicknessis calculated on the assumption that all of the TFSA remains on the areaof interface between oil and water on which the product or its solutionin a volatile solvent has been placed. Since spreading pressure isnumerically equal to the change in interfacial tension resulting fromspreading of a film, it is conveniently determined by making interfacialtension measurements before and after adding a known amount of TFSA toan interface of known area.

Alternatively, one may utilize an interfacial film balance of theLangmuir type such as that described by J. H. Brooks and B. A. Pethica,Transactions of the Faraday Society (1964), p. 20 et seq, or othermethods which have been qualified for such interfacial spreadingpressure determinations.

In determining the interfacial spreading pressure of the TFSA products,I prefer to use as the oil phase a fairly available and reproducible oilsuch as a clear, refined mineral oil. Such oils are derived frompetroleum and have been treated with sulfuric acid and other agents toremove nonhydrocarbon and aromatic constituents. Typical of such oils is"Nujol", distributed by Plough, Inc. This oil ranges in density fromabout 0.85 to 0.89 and usually has a solubility parameter between about6.9 and about 7.5. Numerous similar oils of greater or smaller densityand viscosity are commonly available from chemical supply houses andpharmacies.

Other essentially aliphatic or naphthenic hydrocarbons of low volatilityare equally usable and will yield similar values of spreading pressure.Suitable hydrocarbon oils appear in commercial trade as refined "whiteoils", "textile lubricants", "paraffin oil", and the like. Frequently,they may contain very small quantities of alpha-tocopherol (Vitamin E)or similar antioxidants which are oil-soluble and do not interfere withthe spreading measurements.

While the existence of micelles and of oily or aqueous micellarsolutions have been known for some time (see, e.g., "Surface Activity",Moilliet, Collie and Black, D. Van Nostrand & Co., New York (1961) andare probably involved in many operations involving detergency whereeither oily (nonpolar) or earthy (highly polar) soil particles are to beremoved, their utility in cooperation with hydrotropic agents for thepresent purposes is an unexpected and unpredictable discovery.

In U.S. Pat. No. 2,356,205, issued Aug. 22, 1944, to Chas. M. Blair, Jr.& Sears Lehman, Jr., a wide variety of micellar solutions designed todissolve petroleum oils, bitumen, wax, and other relatively nonpolarcompounds are described for purposes of cleaning oil formation faces andfor effecting enhanced recovery of petroleum by solution thereof. Atthis early date, however, the use of micellar principles was notcontemplated for the preparation of solutions of the relatively highmolecular weight demulsifiers.

However, some of the principles disclosed in the above patent, omittingthe main objective therein of dissolving relatively large amounts ofhydrocarbons, chlorinated hydrocarbons, and the like, are applicable topreparation of the present compositions.

The four necessary components of the micellar solutions of TFSA are:

1. A micelle-forming amphipathic agent. Such may be anionic, cationic,or nonionic and, if anionic or cationic, may be either in salt form oras the free acid or free base or mixtures thereof.

2. A hydrotropic agent. This is a small to medium molecular weightsemi-polar compound containing oxygen, nitrogen or sulfur and capable offorming hydrogen bonds. It is believed that such agents cooperate insome manner with the amphipathic agent to form clear or opalescent,stable compositions.

3. Water.

4. TFSA, having the properties recited above.

In addition to these components, the micellar solutions may contain, butare not required to contain, salts, hydrocarbons, or small amounts ofother inorganic or organic material. Such constituents may beimpurities, solvents, or by-products of syntheses used in forming thehydrotropic agent, or may be additions found useful in forming thecomposition of this invention. As an example of the latter, smallamounts of inorganic salts such as NaCl, Na₂ SO₄, KNO₃, CaCl₂, and thelike, are sometimes helpful in promoting homogeneity with a minimum ofamphipathic and hydrotropic agents. They may also yield compositions oflower freezing point, a property useful when the composition is employedin cold climates. Similarly, ethylene glycol, methanol, ethanol, aceticacid, or similar organic compounds may be incorporated into thecompositions to improve physical properties such as freezing point,viscosity, and density, or to improve stability.

As stated above, the micelle-forming amphipathic agents which may beused in preparing the aqueous solutions herein contemplated may beeither cation-active, anion-active, or of the nonelectrolytic type.Amphipathic agents generally have present at least one radicalcontaining about 10 or more carbon atoms and not more than about 64carbon atoms per molecule. This is true of the amphipathic agentsemployed in the present invention as a component of the vehicle orsolvent or dispersant employed in the present compositions. Thehydrophobic portions of these agents may be aliphatic, alicyclic,alkylalicyclic, aromatic, arylalkyl, or alkylaromatic. The preferredtype of agents are those in which the molecule contains a long,uninterrupted carbon chain containing from 10 to 22 carbon atoms inlength. Examples of suitable anion-active amphipathic agents include thecommon soaps, as well as materials such as sodium cetyl sulfate,ammonium lauryl sulfonate, ammonium di-isopropyl naphthalene sulfonate,sodium oleyl glyceryl sulfate, mahogany and green sulfonates frompetroleum or petroleum fractions or extracts, sodium stearamidoethylsulfonate, dodecylbenzene sulfonate, dioctyl sodium sulfosuccinate,sodium naphthenate, and the like. Other suitable sulfonates aredisclosed and taught in U.S. Pat. No. 2,278,171, issued Feb. 17, 1942,to De Groote and Keiser.

Suitable cation-active compounds include cetyl pyridinium chloride,stearamidoethyl pyridinium chloride, trimethyl-heptadecyl ammoniumchloride, dimethyl-pentadecyl sulfonium bromide, octadecylamine acetate,and 2-heptadecyl-3-diethylene diaminoimidazoline diacetate.

Suitable nonelectrolytic amphipathic agents include the oleic acid esterof nonaethylene glycol, the steric acid ester of polyglycerol,oxyethylated alkylphenols, and long chain alcohol ethers of polyethyleneglycols.

It is of course, well known that amphipathic compounds are readily andcommercially available, or can be readily prepared to exhibit thecharacteristics of more than one of the above mentioned types. Suchcompounds are disclosed in U.S. Pat. No. 2,262,743, dated Nov. 11, 1941,to De Groote, Keiser and Blair. For convenience, in such instances wherea surface-active material may show the characteristics of more than oneof the above described types, it is understood that it may be classifiedunder either or both types.

The mutual solvent or hydrotropic agents of the solution utilized in thepresent invention are characterizable as compounds of a hydrophobichydrocarbon residue of comparatively low molecular weight combined witha hydrophilic group of low molecular weight and are free fromsurface-active properties. The hydrophobic residue may contain from 2 to12 carbon atoms and may be alkyl, alicyclic, aromatic, or alkylsubstituted alicyclic or aromatic, or may be the hydrocarbon portion ofa heterocyclic or hydrocarbon substituted heterocyclic group. Thehydrocarbon residue may have branched or normal chain structure, but nobranch may have a length of more than 7 carbon atoms from the point ofattachment to the hydrophilic residue, counting a benzene or cyclohexylgroup as being equivalent in length to an aliphatic chain of threecarbon atoms. Where the hydrocarbon residue consists of not more than 4carbon atoms, structures of the normal primary alkyl type are preferred.Where the residue is made up of more than four carbon atoms, thenstructures of secondary and tertiary types are also good where thesecond and third branches may be methyl or ethyl groups.

This hydrophobic hydrocarbon residue is combined either directly orindirectly with a hydrophilic group of one of the following groups:

(a) A hydroxyl group which may be alcoholic, phenolic, or carboxylic;

(b) An aldehyde group;

(c) A carboxy amide group;

(d) An amine salt group;

(e) An amine group; and

(f) An alkali phenolate group.

By "indirectedly combined with one of these groups" is meant that thehydrocarbon residue is combined as by etherification, esterification, oramidification, or the like, with another organic residue which containsnot more than four carbon atoms and also one or more of the hydrophilicgroups named above, provided that after said combination, at least oneof the hydrophile groups remains free. Specific examples illustratingthis class of compounds are: Ethyl alcohol, n-amyl alcohol,alphaterpineol, p-cresol, cyclohexanol, n-butyraldehyde, benzaldehyde,n-butyric acid, glycol mono-butyrate, propyl lactate, mono n-butyl aminehydrochloride, n-propionamid, ethylene glycol mono n-butyl aminehydrochloride, n-propionamid, ethylene glycol mono n-butyl ether,pyridine, methylated pyridine, piperidine, or methylated piperidines.

The solubilizer (mutual solvent or hydrotropic compound above described)is essentially a semi-polar liquid in the sense that any liquid whosepolar character is no greater than that of ethyl alcohol and which showsat least some tendency to dissolve in water, or have water dissolved init, is properly designated as semi-polar.

The solubilizer or semi-polar liquid indicated may be illustrated by theformula X - Z, in which X is a radical having 2 to 12 carbon atoms, andwhich may be alkyl, alicyclic, aromatic, alkylalicyclic, alkylaryl,arylalkyl, or alicyclicalkyl in nature, and may, furthermore, includeheterocyclic compounds and substituted heterocyclic compounds. There isthe added limitation that the longest carbon atom chain must be lessthan eight carbon atoms, and that, in such characterization, cycliccarbon atoms must be counted as one-half. Z represents: --OH; ##STR1##--COOH; or --OMe where U and V are hydrogen or a hydrocarbon substituentand Me is an alkalie metal; ##STR2## if X is a cyclic teritary aminenucleus; ##STR3## if X is a cyclic secondary amine nucleus.

The semi-polar liquid also may be indicated by the following formula:X--Y--R--(Z)_(n). Here X and Z have their previous significance, R is--CH₂ --,--C₂ H₄ --,--C₃ H₅ ═, --C₃ H₆ --or --C₂ H₄ --O--C₂ H₄ --and nis either one or two as the choice of R demands. Y is one of thefollowing: ##STR4##

In general, these hydrotropic agents are liquids having dielectricconstant values between about 6 and about 26, and have at least onepolar group containing one or more atoms of oxygen, and/or nitrogen. Itis significant, perhaps, that all of the solubilizers are of types knownto be able to form hydrogen bonds.

The choice of solubilizer or common solvent and its proportion in themixture depends somewhat upon the amphipathic agent used, the amount andkind of TFSA used, and the proportion of water used, and is bestdetermined by preparing experimental mixtures on a small scale.

In some cases, it is desirable to include in the solution small amountsof acid, alkali, or inorganic salts, as it has been found that thepresence of these electrolytes often gives solutions having greaterstability and a wider range of miscibility with water and organicmaterial. Excess acid, when used, will usually be in solutionscontaining a cation-active or nonelectrolytic wetting agent, but notexclusively so. Excess alkali, when used, will usually be in a solutioncontaining anion-active wetting agents, but, again not exclusively.

The acylated polyether polyol or TFSA utilized in this invention isgenerally an organic polymer or semi-polymer with an average molecularweight above about 800 and below about 30,000 and has a structure whichwill allow orientation on polar surfaces with much or most of theelements of the molecule in a thin plane. To be effectively adsorbed atoil-water or oil-rock interfaces and subsequently to be desorbed atwater-rock interfaces, the TFSA must generally contain constituentswhich give it a highly distributed hydrophile and hydrophobe character,and without such concentrations of either hydrophilic or hydrophobicgroups as to produce water solubility or oil solubility, in the ordinarymacroscopic sense. The TFSA also appears to differ from formerly usedsurfactants in that the effects on oil-water interfacial tensions as afunction of concentration are limited. While spreading efficiently atsuch interfaces to form thin films with spreading pressures up to about35 to 40 dynes per cm, addition or larger amounts of TFSA haverelatively little effect on interfacial tension. Also, the present TFSAconstituent of the micellar solution in contrast to formerly usedsurfactants, has relatively little or no tendency to stabilize eitheroil-in-water or water-in-oil emulsions when present in normal useamounts.

Usually the TFSA constituents applicable to the practice of theinvention are organic molecules containing carbon, hydrogen and oxygen,although in some instances, they may also contain sulfur, nitrogen,silicon, chlorine, phosphorous or other elements. Small amounts ofinorganic material such as alkalies, acids or salts may appear in thecompositions as neutralizing agents, catalyst residues or otherwise. Thecritical requirements for the TFSA compositions are not so muchcompositional as structural and physical. They must be made up ofhydrophilic (polar) moieties, usually ones capable of forming hydrogenbonds, such as hydroxyl, carbonyl, ester, ether, sulfonium, amino,ammonium, phospho or similar hydrogen bonding groups, connected by or tohydrophobic groups, such as alkylene, alkyl, cycloaklyl, aryl, arylene,aralkyl, polyalkylene, polyalkylyne, combinations of such groups andsuch groups containing relatively non-polar substituents, such ashydrocarbon, chlorine, fluorine and the like. Sometimes the hydrophobicmoieties are larger and contain more atoms than the polar groups in themolecular, having a minimum of two carbon atoms in each group and up toas many as 36 carbon atoms, although the actual ratio of sizes dependsgreatly on the structure of the hydrophilic moiety. Most commonly, thehydrophobic groups will contain 14 to 22 carbon atoms and will havelinear or sheet-like conformations allowing for relatively flatorientation on surfaces.

Polar moieties other than hydrogen bonding ones are not excluded fromthese compositions and, indeed, may be deliberately included in somestructures to improve adsorption and interfacial spreading tendencies.For example, quaternary ammonium groups, while incapable of forminghydrogen bonds, can improve spreading and interfacial adsorption in someapplications by way of their highly ionized form which imparts cationiccharacter to the molecules in which they occur and, via coulombicrepulsion effects, can improve spreading in a film.

Generally, the TFSA constituents will contain at least two each of therequired hydrophilic (polar) and hydrophobic moieties per molecule andcommonly will contain many more of each. The effective products,however, must have the three properties described above.

While, as pointed out above, the effective TFSA may be derived from awide variety of chemical reactants and may contain numerous differentgroups or moieties, I have found that particularly effective productsare those which are described as an acylated polyether polyol having theformula: ##STR5## wherein: A is an alkylene oxide group, --C_(i) H_(2i)O--;

O is oxygen;

i is a positive integer from 2 to about 10;

j is a positive integer no greater than about 100;

k is a positive integer no greater than about 100;

N is nitrogen;

R¹ is one of hydrogen, a monovalent hydrocarbon group containing lessthan about C₁₁, or [A_(L) H];

L is a positive integer no greater than about 100;

R is a hydrocarbon moiety of a polyol, a primary or secondary amine, aprimary or secondary polyamine, a primary or secondary amino alcohol, orhydrogen; and

m÷n is no greater than about 4 when R is other than hydrogen and one ofm and n is zero and the other is unity when R is hydrogen,

said acylated polyether polyol being the reaction product of saidpolyether polyol and a member selected from the class consisting ofmono- and polybasic carboxylic acids, acid anhydrides, and iso-, diiso-,and polyisocyanates, said acylated polyether polyol at about 25° C.: (a)being less than about 1% by volume soluble in water and in isooctane;(b) having a solubility parameter in the range of between about 6.9 andabout 8.5; and (c) spreading at the interface between distilled waterand refined mineral oil to form a film having a thickness no greaterthan about 20 Angstroms at a film pressure of about 16 dynes per cm.

Alternatively, the TFSA constituents may be described as acylatedpolyether polyols derivable by the reaction of an alkylene oxidecontaining less than about 10 carbon atoms with a member of the groupconsisting of polyols, amines, polyamines and amino alcohols containingfrom between about 2 to about 10 active hydrogen groups capable ofreaction with alkylene oxides and the acylating agent being a memberselected from the class consisting of mono- and polybasic carboxylicacids, acid anhydrides and iso-, diiso- and polyisocyanates.

Compositions incorporated within the scope of the formula set forthabove contain an average of about 11/2 or more hydroxyl groups permolecule and are generally composed of a cogeneric mixture of productsobtained by condensing alkylene oxides with smaller molecules containingtwo or more reactive hydrogens as part of hydroxyl or amino groups.

Representative of these compositions is polypropylene glycol, having anaverage molecular weight of about 1,200, to which about 20% by weight ofethylene oxide has been added. Such a polyether glycol is theoreticallyobtainable by condensing about 20 moles of propylene oxide with aboutone mole of water, followed by addition of about six moles of ethyleneoxide. Alternatively, one may condense about 20 moles of propylene oxidewith a previously prepared polyethylene glycol of about 240 averagemolecular weight.

Alkylene oxides suitable for use in preparing the TFSA constituents usedin the present solutions include ethylene oxide, propylene oxide,butylene oxide, 2-3-epoxy-2-methyl butane, trimethylene oxide,tetrahydrofuran, glycidol, and similar oxides containing less than about10 carbon atoms. Because of their reactivity and relatively low cost,the preferred alkylene oxides for preparing effective TFSA constituentsare the 1,2-alkylene oxides (oxiranes) exemplified by ethylene oxide,propylene oxide and butylene oxide. In the preparation of many TFSAconstituents, more than one alkylene oxide may be employed either asmixtures of oxides or sequentially to form block additions of individualalkylene oxide groups.

Other suitable dihydric alcohols may be obtained by condensing alkyleneoxides or mixtures of oxides or in successive steps (blocks) withdifunctional (with respect to oxide addition) compounds, such asethylene glycol, methyl amine, propylene glycol, hexamethylene glycol,ethyl ethanolamine, analine, resorcinol, hydroquinone and the like.

Trihydric ether alcohols may be prepared by condensation of ethylene,propylene or butylene oxides with, for example, glycerin, ammonia,triethanolamine, diethanolamine, ethyl ethylene diamine or similarsmaller molecules containing three hydrogens capable of reacting withalkylene oxides. Similarly, polyether alcohols with a multiplicity ofhydroxyl groups may be obtained by condensing alkylene oxides withmultireactive starting compounds, such as pentaerythritol, glycerol,N-monobutyl ethylene diamine, trishydroxymethylaminomethane, ethylenediamine, diethylenetriamine, diglycerol, hexamethylene diamine,decylamine and cyclohexylamine. DeGroote, in U.S. Pat. No. 2,679,511,describes a number of amino derived polyols which he subsequentlyesterfies. Product 15-200, manufactured and sold by the Dow ChemicalCompany, and derived by oxyalkylation of glycerol with a mixture ofethylene and propylene oxides, is an example of a commercially availablepolyol of the kind contemplated herein.

Generally, these compositions will have average molecular weights of15,000 or less and will be derived from reactive hydrogen compoundshaving 18 or fewer carbon atoms and 10 or fewer reactive hydrogens.

Other general descriptions of suitable compounds coming within the scopeof the structure detailed above, along with methods for carrying out theactual manufacturing steps, are disclosed in "High Polymers, Vol. XIII,Polyethers," edited by N. G. Gaylord, John Wiley & Sons, New York, 1963.

Effective TFSA with improved performance may be prepared by acylation ofthe polyether polyol described above with a mono- or polybasiccarboxylic acid, acid anhydride, isocyanate, diisocyanate or otherpolyisocyanate. An especially useful TFSA may be made by reacting anapproximately difunctional polyether polyol with a difunctionalcarboxylylic acid, acid anhydride or isocyanate to form a polymericester or urethane. However, polymerization is not always required, andwhere effected is usually not carried to the point of including a verylarger number of monomer units in the molecule. Frequently, effectivereagents are obtained where residual, unreacted hydroxyl or carboxylgroups remain in the product or, where a polyisocyanate is used, one ormore residual isocyanate groups or amino or substituted urea groupswhich result from reaction of residual end groups with water, followedby decarboxylation, may remain.

Examples of acylating agents suitable for preparing useful estersinclude acetic acid, acetic anhydride, butyric acid, benzoic acid,abietic acid, adipic acid, diglycollic acid, phthallic anhydride,fumaric acid, hydroxyacetic acid, itaconic acid, succinic acid,dimerized fatty acids and the like. I have found the most generallyuseful acylating agents to be the di- and mono-basic acids andanhydrides containing less than 13 carbon atoms.

Examples of isocyanates useful for the acylation of a polyether polyolto produce an effective TFSA include methylisocyanate, phenylisocyanate, cyclohexylmethylene isocyanate, and the like. Especiallyuseful reactants are polyisocyanates containing two or more isocyanategroups and including phenylene diisocyanate, toluene diisocyanate,diphenylmethane diisocyanate, hexamethylene diisocyanate,1,5-Naphthalene diisocyanate and polymethylenepolyphenyl isocyanates.

Following acylation reactions of polyether polyols with polyisocyanates,where a stoichiometric excess of the latter reactant is employed,remaining isocyanate groups may be left as such or may, be appropriateaddition of water or monohydric alcohol, be converted to carbamic acidgroups, which immediately undergo decarboxylation to yield residualamino groups, or carbamate groups.

Examples of acylated polyether polyols and their manufacturingprocedures are well known to the art, as disclosed in U.S. Pat. Nos.2,454,808, issued Nov. 30, 1948, to Kirkpatrick, 2,562,878, issued Aug.7, 1951, to Blair, 2,679,511, issued May 25, 1954, to DeGroote,2,602,061, issued July 1, 1952, also to DeGroote, "Chemical ProcessIndustries" by R. N. Shreve, McGraw Hill Publishing Co., 1967, page 654et seq., and "High Polymers", Vol. XIII, edited by N. G. Gaylord, JohnWiley & Sons, 1963, page 317 et seq., the disclosure of each of which ishereby incorporated by reference.

As to the limits of the various constituents of the micellar solutionscontaining TFSA, the following will serve as a guide, the percentagesbeing by weight:

    ______________________________________                                                         Percent                                                      ______________________________________                                        TFSA Constituents  about 5 to about 75                                        Hydrotropic Agent  about 2 to about 30                                        Amphipathic Agent  about 2 to about 30                                        Water              about 15 to about 90                                       ______________________________________                                    

Although the exact function of the electrolytes previously referred tois not completely understood, the effect, in part, may be due to theability to bind water, i.e., to become hydrated. This suggests thatcertain other materials which are highly hydrophile in character andclearly differentiated from the classes of non-polar solvents andsemi-polar solubilizers may be the functional equivalent of anelectrolyte. Substances of this class which ordinarily do not dissociateinclude glycerol, ethylene glycol, diglycerol, sugar, glucose, sorbitol,mannitol, and the like.

Also, as stated above, these solutions may contain other organicconstituents such as hydrocarbons. These frequently are used as thinningagents, azetropic distillation aids or reflux temperature controllers inthe manufacture of the TFSA constituent and may be left therein when thepresent micellar solutions are prepared. To the extent that suchcompounds are present they appear to compete somewhat with the TFSAconstituent for micelle space, thus limiting, to some extent, themaximum amount of TFSA constituent which can be brought into homogeneoussolution.

Selection of an effective TFSA composition for a given petroleumemulsion and determination of the amount required is usually made byso-called "bottle tests", conducted, in a typical situation, as follows:

A sample of fresh emulsion is obtained and 100 ml portions are pouredinto each of several 180 ml screw top prescription or similar graduatedbottles. Dilute solutions (1% or 2%) of various TFSA constituents areprepared in isopropyl alcohol. By means of a graduated pipette, a smallvolume of a TFSA solution is added to a bottle. A similar volume of eachcomposition is added to other bottles containing emulsion. The bottlesare then closed and transferred to a water bath held at the sametemperature as that employed in the field treating plant. After reachingthis temperature, the bottles are shaken briskly for several minutes.

After the shaking period, the bottles are placed upright in the waterbath and allowed to stand quietly. Periodically, the volume of theseparated water layer is recorded along with observations on thesharpness of the oil-water interface, appearance of the oil and clarityof the water phase.

After the standing period, which may range from 30 minutes to severalhours, depending upon the temperature, the viscosity of the emulsion andthe amount of TFSA compositions used, small samples of the oil areremoved by pipette or syringe and centrifuged to determine the amount offree and emulsified water left in the oil. The pipette or syringe usedto remove the test samples should be fitted through a stopper or otherdevice which acts as a position guide to insure that all bottles aresampled at the same fluid level.

The combined information on residual water and emulsion, speed of thewater separation and interface appearance provides the basis forselection of the generally most effective TFSA constituent. Where noneof the results are satisfactory, the tests should be repeated usinghigher concentrations of TFSA constituents and, conversely, where allresults are good and similar, the tests should be repeated at lowerconcentrations until good discrimination is possible.

In practicing the process for resolving petroleum emulsions of thewater-in-oil type with the present micellar solution, such solution isbrought into contact with or caused to act upon the emulsion to betreated, in any of the various methods or apparatus now generally usedto resolve or break petroleum emulsions with a chemical reagent, theabove procedure being used alone or in combination with otherdemulsifying procedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in atank and conduct a batch treatment type of demulsification procedure torecover clean oil. In this procedure, the emulsion is admixed with themicellar TFSA solution, for example, by agitating the tank of emulsionand slowly dripping the micellar TFSA solution into the emulsion. Insome cases, mixing is achieved by heating the emulsion while dripping inthe micellar TFSA solution, depending upon the convection currents inthe emulsion to produce satisfactory admixture. In a third modificationof this type of treatment, a circulating pump withdraws emulsion from,e.g., the bottom of the tank and reintroduces it into the top of thetank, the micellar TFSA solution being added, for example, at thesuction side of said circulating pump.

In a second type of treating procedure, the micellar TFSA solution isintroduced into the well fluids at the wellhead, or at some pointbetween the wellhead and the final oil storage tank, by means of anadjustable proportioning mechanism or proportioning pump. Ordinarily,the flow of fluids through the subsequent lines and fittings suffices toproduce the desired degree of mixing of micellar TFSA solution andemulsion, although, in some instances, additional mixing devices may beintroduced into the flow system. In this general procedure, the systemmay include various mechanical devices for withdrawing free water,separating entrained water, or accomplishing quiescent settling of thechemically treated emulsion. Heating devices may likewise beincorporated in any of the treating procedures described herein.

A third type of application (down-the-hole) of micellar TFSA solution toemulsion is to introduce the micellar solution either periodically orcontinuously in diluted form into the well and to allow it to come tothe surface with the well fluids, and then to flow thechemical-containing emulsion through any desirable surface equipment,such as employed in the other treating procedures. This particular typeof application is especially useful when the micellar solution is usedin connection with acidification of calcareous oil-bearing strata,especially if dissolved in the acid employed for acidification.

In all cases, it will be apparent from the foregoing description, thebroad process consists simply in introducing a relatively smallproportion of micellar TFSA solution into a relatively large proportionof emulsion, admixing the chemical and emulsion either through naturalflow, or through special apparatus, with or without the application ofheat, and allowing the mixture to stand quiescent until the undesirablewater content of the emulsion separates and settles from the mass.

Besides their utility for breaking petroleum emulsions, the presentmicellar TFSA solutions, as mentioned earlier, may be used to preventemulsion formation in steam flooding, in secondary waterflooding, inacidizing of oil-producing formations, and the like.

Petroleum oils, even after demulsification, may contain substantialamounts of inorganic salts, either in solid form or as small remainingbrine droplets. For this reason, most petroleum oils are desalted priorto refining. The desalting step is effected by adding and mixing withthe oil a few volume percentages of fresh water to contact the brine andsalt. In the absence of demulsifier, such added water would also becomeemulsified without effecting its washing action. The present micellarsolutions may be added to the fresh water to prevent its emulsificationand to aid in phase separation and removal of salt by the desaltingprocess. Alternatively, if desired, they may be added to the oil phaseas are present aromatic solvent compositions.

Most petroleum oil, along with its accompanying brines and gases, iscorrosive to steel and other metallic structures with which it comes incontact. Well tubing, casing, flow lines, separators and lease tanks areoften seriously attached by well fluids, especially where acidic gasessuch as H₂ S or CO₂ are produced with the liquids, but also in systemsfree of such gases.

It has been known for some time, and as exemplified in U.S. Pat. No.2,466,517, issued Apr. 5, 1949, to Chas. M. Blair and Wm. F. Gross, thatsuch corrosive attack of crude oil fluids can be mitigated or preventedby addition to the fluids of small amounts of organic inhibitors.Effective inhibitors compositions for this use are usually semi-polar,surface active compounds containing a nonpolar hydrocarbon moietyattached to one or more polar groups containing nitrogen, oxygen orsulfur or combinations of such elements. Generally these inhibitors ortheir salts are soluble in oil and/or water (brine) and frequentlyappear to be able to form micelles in one or both of these phases.Typical inhibitors include amines such as octyl amine, dodecyl amine,dioctodecyl amine, butyl naphthyl amine, dicyclohexyl amine, benzyldimethyldodecyl ammonium chloride, hexadecylaminopropyl amine,decyloxypropyl amine, mixed amines prepared by hydrogenation of nitrilederivatives of tall oil fatty acids, soya acid esters of monoethanolamine, 2-undecyl, 1-amino ethyl imidazoline and a wide variety ofcationic nitrogen compounds of semi-polar character. Also effective insome applications are nonyl succinic acid, diocylnaphthalene sulfonicacid, trimeric and dimeric fatty acids, propargyl alcohol,mercaptobenzothiozole, 2, 4, 6-trimethyl-1, 3, 5-trithiaane,hexadecyldimethyl benzimidazolium bromide,2-thiobutyl-N-tetrodecylpyridinium chloride,tetrahydronaphthylthiomorpholine, and the like.

In contrast to the TFSA, corrosion inhibitors appear to function byforming on the metal surface strongly adherent, thick, closely packedfilms which prevent or lessen contact of corrosive fluids and gases withthe metal and interfere with ionic and electron transfer reactionsinvolved in the corrosion process.

Corrosion inhibitors are quite commonly introduced down the casingannulus of oil wells where they commingle with the well fluids beforetheir travel up the well tubing and thus can effectively preventcorrosion of well equipment. Where corrosive attack occurs at thesurface, the inhibitor may be introduced at or near the well head,allowing it to adsorb on the flow lines and surface equipment to insureprotection.

Addition of inhibitor at either downhole or surface locations may becombined conveniently with demulsifier addition since the latter is alsofrequently introduced in one of these locations.

Inhibitors such as those mentioned above, may generally be incorporatedinto the TFSA micellar solutions, replacing a portion of or in additionto the TFSA constituent. Also, since many of these inhibitors arethemselves micelle-forming amphipathic agents, they may be included inthe micellar solution as such, replacing other amphipathic agents whichmight be otherwise utilized. Combining the micellar solution withcorrosion inhibitor permits more economic chemical treatment by reducinginventory to one compound, requiring only one chemical injection systemrather than two and lessening the labor and supervision required.

Still another important effect of using the micellar solution of TFSAand corrosion inhibitor results from the prevention of emulsification bythe inhibitor. Frequently, it has been found that inhibitor in theamount required for effective protection causes the formation of veryrefractive emulsions of water and hydrocarbon, especially in systemscontaining light, normally nonemulsifying hydrocarbons such asdistillate, casing head gasoline, kerosene, diesel fuel and variousrefinery fractions. Inhibitors are commonly used in refinery systemswhere emulsification is highly objectionable and where the compositionscould be designed to include an effective emulsion preventative micellarsolution of TFSA.

Inhibitor use may range from a few to several hundred parts per millionbased on the oil to be treated, depending upon the severity ofcorrosion. For a given oil field or group of wells, tests will normallybe run to determine the requirement for micellar solution of TFSA andfor inhibitor and a composition incorporating these components inapproximately the desired ratio will be prepared. In some instances, therequirement for micellar solution of TFSA in the best concentration mayresult in use of corrosion inhibitor, employed as micelle-former, insome excess over that required for inhibition. This will not affect theutility of the micellar solution and will provide a comfortable excessof inhibition which can be helpful during the periods when highercorrosivity may be encountered.

Examples of micellar solutions employing TFSA with inhibitor in waterdispersible, micellar solutions are given below.

Selection of the proper corrosion inhibitor for a given system or oil isusually made by conducting laboratory tests under conditions simulatingthose encountered in the well or flowline. Such tests are exemplified bythat described in Item No. 1K155, "Proposed Standardized LaboratoryProcedure for Screening Corrosion Inhibitors for Oil and Gas Wells",published by the National Association of Corrosion Engineers, Houston,Texas.

EXAMPLES OF THIN FILM SPREADING AGENTS EXAMPLE I

Reference is made to U.S. Pat. No. 2,562,878, dated Aug. 7, 1951, toChas. M. Blair, Jr., which describes the preparation of demulsifierswhich are polyesters of dicarboxylic acids and polyhydric alkylene etherglycols. Using the procedure described therein, 150 lbs. of diglycolicacid was reacted with 2,000 lbs. of "Pluronic L-62" manufactured byWyandotte Chemical Corporation of Wyandotte, Michigan. "Pluronic L-62"is described as a polypropylene glycol having a molecular weight ofabout 1,650 to which has been added and condensed therewith about 25% byweight of ethylene oxide.

The esterification reaction was continued until the acid number of thereaction mixture had dropped to about 15.

The resulting product was a moderately viscous liquid, insoluble to theextent of 1% in either water or isooctane, had a Solubility Parameter of8.1, and spread at the interface between white mineral oil and water at25° C. to yield a film pressure of 22 dynes per cm at a calculatedthickness of 14 Angstroms.

EXAMPLE II

Using the procedure described by C. H. M. Roberts in U.S. Pat. No.1,977,146, dated Oct. 23, 1934, one mole each of the mono- anddiglycerides of ricinoleic acid were reacted with three moles ofphthallic anhydride. The reaction was stopped short of gelation to yielda viscous, reddish polymer, insoluble in water and isooctane, having asolubility parameter of 8.4 and spreading at the white oil-distilledwater interface with a pressure of 20 dynes per cm at a calculatedthickness of 10 Angstroms.

EXAMPLE III

To 1,000 parts of commercial polyoxypropylene glycol of molecular weightof about 2,000 was added 200 parts of ethylene oxide. Reaction wasconducted as in Example I. After completion of the ethylene oxideaddition, a mild vacuum was applied for 30 minutes to remove anyunreacted oxide. The temperature was lowered to 40° C. and 5 parts ofdodecylbenzene sulfonic acid were added to the reaction mass whilestirring. Eighty parts of phenyacetic acid were then introduced andheating and stirring were commenced under a take-off condensor. Thetemperature was slowly raised to about 160° C. over a three-hour periodand was held at this temperature for an additional 2 hours.

The product was then cooled and drummed. It was an effective demulsifierespecially for petroleum emulsions encountered in southern Louisiana,and met the criteria recited previously for such interfacially activecompounds.

EXAMPLE IV

Two and one-half parts of tris-hydroxymethylaminomethane weresubstituted for the dipropylene glycol in Example I of my co-pendingapplication Ser. No. 082,349, filed Oct. 5, 1979, entitled "PetroleumDemulsifiers Comprising A Polyether Polyol", the disclosure of which isherein incorporated by reference.

To the above product was added with stirring 5 parts of maleicanhydride. The temperature was then raised to 130° C. while the vesselwas open to a take-off condensor. Stirring and heating were continueduntil a sample of the reaction mass had a viscosity in the range of 900to 1,100 centipoises at 80° C.

This product was an effective thin film spreading agent and especiallyuseful as a demulsifier for petroleum emulsions occurring in westernKansas and in Kuwait.

EXAMPLE V

Using the apparatus and procedure of Example I, 4,000 lbs. ofpolypropylene glycol of average molecular weight 1,200 was condensedwith 700 lbs. of ethylene oxide. Forty pounds of potassium hydroxide wasdissolved in the polypropylene glycol prior to oxide addition, which wascarried out within the temperature range of about 140°-160° C. under amaximum pressure of about 75 psi.

After completion of the above reaction, the temperature was lowered toabout 60° C. and the reaction vessel was connected to a take-offcondensor. Fifty pounds of 85% phosphoric acid was slowly added to thereaction mass with stirring followed by 314 lbs. of adipic acid. Thetemperature was then slowly brought to 145°-155° C. while continuing tostir and to distill water from the reaction mixture. The acid number ofthe product was periodically determined. When a valve between 10 and 15mg. KOH per gm. was reached, heating was stopped, the product was cooledto room temperature and filled into 55-gallon drums.

This product has a calculated equivalent weight in excess of 4,000, isinsoluble to the extent of 1% in water and isooctane, has a solubilityparameter of 7.9 and rapidly spreads at the interface between white oiland distilled water, at 25° C., to give a film pressure of 18 dynes percm at a calculated thickness of 18 Angstroms.

EXAMPLE VI

Into a 1,000 gal. stainless steel autoclave, equipped with steam jacket,internal cooling coils, stirrer, condensor and several inlet feed lineswere place 92 lbs. of glycerol. 2,750 lbs. of a mixture of 2,250 lbs. ofpropylene oxide and 500 lbs. of ethylene oxide was prepared in aseparate weighed feed tank. Twelve pounds of a 50% aqueous solution ofpotassium hydroxide was stirred into the glycerol while heating to about120° C. During this period, the vessel was connected to a steam jetvacuum system through the condensor, arranged in take-off position.Stirring under vacuum was continued until the evolution of water hadeffectively ceased.

The vessel was then closed and the mixed oxides were introduced slowly.The resulting exothermic reaction was controlled by the oxide additionrate such as to allow a slow increase in temperature to about 150° C.After the addition of about 800 lbs. of oxides the rate of reactiondeclined. The oxide addition line was then closed, the temperaturelowered to 110° C., the vessel was vented briefly to the vacuum jet, andan additional 25 lbs. of 50% aqueous solution of potassium hydroxide wasintroduced into the reaction mass which was then stirred under vacuum at120°-140° C. until water evolution ceased.

The vessel was closed, the oxide inlet line was again opened andreaction was continued with the fresh catalyst, holding the temperatureat about 150° C. under a maximum pressure of about 50 psi until thewhole of the 2,750 lbs. of mixed oxide had been reacted.

After cooling this batch to about 120° C., 1,860 lbs. of commercialmixed xylene was pumped into the autoclave and the whole was stirred andadjusted to a temperature of about 95° C. A solution of 125 lbs. oftoluene diisocyanate in 200 lbs. of xylene was then slowly pumped intothe vessel while maintaining the temperature at 100°±5° C. forapproximately the two hours required for the addition. The temperaturewas then raised to 140° C. and stirring was continued until theviscosity at 100° C. was within the range of 1,000 to 1,500 centipoises.Heating was then discontinued and the batch was cooled quickly to allowtransfer to storage.

A sample of this product, after removal of xylene by vacuum distillationwas found to meet the three criteria for a TFSA.

EXAMPLES OF MICELLAR SOLUTIONS OF TFSA's EXAMPLE A

    ______________________________________                                                                Wt. %                                                 ______________________________________                                        Product of Example II     40                                                  2-heptadecyl-3-triethylene triaminoimidazoline                                                          6                                                   Acetic Acid               1.5                                                 Phenol                    2.5                                                 n-Butanol                 10                                                  Water                     40                                                  ______________________________________                                    

Besides having good demulsification action, this product is an effectivecorrosion inhibitor for down-the-hole use, the imidazoline used as theamphipathic agent being a strongly adsorbed inhibitor for steel inanaerobic systems.

EXAMPLE B

    ______________________________________                                                            Wt. %                                                     ______________________________________                                        Product of Example IV 20                                                      n-Dodecylbenzene sulfonic acid                                                                      6                                                       Methanol              14                                                      Ethylene glycol monobutyl ether                                                                     10                                                      Water                 50                                                      ______________________________________                                    

This clear, homogeneous solution is quite acidic. It can be combinedwith 15% hydrochloric acid used for acidizing calcareous oil-producingformations and acts therein to prevent emulsification of acid and spentacid.

EXAMPLE C

    ______________________________________                                                        Wt. %                                                         ______________________________________                                        Product of Example II                                                                           70                                                          Oleyl amine       10                                                          Acetic Acid       3                                                           n-Propanol        2                                                           Water             15                                                          ______________________________________                                    

This is a clear, homogeneous but viscous solution.

EXAMPLE D

    ______________________________________                                                          Wt. %                                                       ______________________________________                                        Product of Example III                                                                            35                                                        Dinonylphenolsulfonic acid                                                                        8                                                         50% Aqueous NaOH    2                                                         Isopropanol         9                                                         Methanol            10                                                        Water               36                                                        ______________________________________                                    

EXAMPLE E

    ______________________________________                                                                Wt. %                                                 ______________________________________                                        Product of Example I      28                                                  Ethyleneglycol monobutyl ether                                                                          14                                                  5-mole ethylene adduct of p-nonyl phenol                                                                14                                                  Water                     44                                                  ______________________________________                                    

This product may be diluted further with water to form clear to slightlyopalescent solutions.

EXAMPLE F

    ______________________________________                                                            Wt. %                                                     ______________________________________                                        Product of Example VI 41.0                                                    Ammonium dodecylbenzene sulfonate                                                                   17.5                                                    Isopropanol           14.0                                                    Water                 17.5                                                    ______________________________________                                    

This product is an effective micellar composition for numerous petroleumemulsions, but is especially effective as a component in synergisticblends with the composition of Example B and with other compositionssuch as those disclosed in my co-pending applications, Ser. Nos.045,479, 45,478, 45,360 and 45,470, cited in detail, above.

The product of Example F has also been found to be an effectivewaterflood additive, especially in combination with aqueous micellarsolutions of resinous polyoxide adducts such as those described in myco-pending application, Ser. No. 082,253, filed Oct. 5, 1979, andentitled, "Micellar Solutions Of Thin Film Spreading Agents ComprisingResinous Polyalkylene Oxide Adducts".

EXAMPLE G

    ______________________________________                                                                Wt. %                                                 ______________________________________                                        Product of Example IV     35                                                  Octaethyleneglycol Monooleate                                                                           10                                                  Ethylene glycol monobutyl ether                                                                         12                                                  "Polyox" coagulant grade (a commercial                                        polyethylene oxide of about                                                   5 million molecular weight)                                                                             2                                                   Water                     41                                                  ______________________________________                                    

This product is a very viscous, redish liquid, readily dispersible inwater to form slightly opalescent solutions. It is effective alone or incombination with other aqueous systems or diluted in water as a floodingagent for oil recovery, especially where a higher viscosity agent isneeded for mobility control.

Further, it is an effective demulsifier for heavy oil emulsion producedin the McKittrick, Ca. field and is even more effective in a 50-50 blendwith the composition of Example E.

Still further, this product is found to assist in the flocculation andsedimentation of finely ground hematite particles during the decantationof aqueous slurries of the ground ore to remove sand and clay mineralsand effect beneficiation of the iron-containing values.

Among procedures which have been found useful in selecting effectivemicellar TFSA solutions for this use, one involves a determination ofoil displacement efficiency from prepared oil-containing rock cores inequipment described below. A tube of glass or transparentpolymethacrylate ester, having an inside diameter of about 3.5 cm (11/2in.) and a length of about 45 cm (18 in.), is fitted with inletconnections and appropriate valves at each end. The tube is mountedvertically on a rack in an air bath equipped with a fan, heater andthermostat which allows selection and maintenance of temperatures in therange of between about 25°-130° C.

To select an effective micellar TFSA solution for use in a given oilformation, samples of the oil, of the producing rock formation and ofthe water to be used in the flooding operation were obtained. Theformation rock is extracted with toluene to remove oil, is dried and isthen ground in a ball mill to the point where a large percentage passesa 40 mesh sieve. The fraction between 60 and 100 mesh in size isretained. The tube described above is removed from the air bath, openedand, after insertion of a glass wool retainer at the lower end, ispacked with the ground formation rock. The tube is tapped gently fromtime-to-time during filling to ensure close packing and is visuallyinspected to assure absence of voids.

The tube is then returned to the air bath, connected to the inlettubing, the temperature is adjusted to the oil formation temperature andwater representative of that produced from the formation is admittedslowly through the bottom line from a calibrated reservoir in an amountjust sufficient to fill the packed rock plug in the tube. This volume isdetermined from the calibrations and is referred to as the "porevolume", being that volume of water just sufficient to fill the pores orinterstices of the packed plug rock.

The upper line to the reservoir is then connected to a calibratedreservoir containing the oil representing that from the formation to beflooded. By proper manipulation of valves, the line is filled with oilwhich is then slowly pumped into the core from the reservoir after thelower valve is opened to allow displacement of the formation water.

As breakthrough of oil at the bottom is noted, pumping is stopped andthe volume of oil introduced into the sand is determined from thereservoir readings. This is referred to as the volume of oil in place.The tube of sand containing oil is then left in the air bath at thetemperature of the formation for a period of three days to allowestablishment of equilibrium between the ground formation rock and theoil with respect to adsorption of oil constituents on the rock andlowering of interfacial tension. The time allowed for equilibrium may bevaried widely. At higher temperatures, the time required to reachequilibrium is probably reduced. Usually, for comparative tests, threedays are allowed to age the oil-rock plug. Results that this procedureclosely simulate work with actual cores of oil-bearing rock.

The oil and water samples used for test purposes are preferably takenunder an inert gas such as high purity nitrogen, and are maintained outof contact with air during all manipulations in order to preventoxidation of the oil and concomitant introduction of spurious polar,surface-active constituents in the oil. At this point, the rock-oilsystem simulates the original oil formation before primary productionoil has commenced and well before any secondary waterflood operation.

The upper inlet line to the tube is now connected to the sample of waterused in the flooding of the oil formation and, by means of a syringepump or similar very small volume positive displacement pump, the wateris pumped into the sand body from the top to displace fluids out of thebottom tubing connection into a calibrated receiver. The pumping rate isadjusted to one simulating the rate of flood water advance in an actualoperation, which is usually in a range of 1 to 50 cm per day. Pumping ismaintained at this rate until two pore volumes of water have been pumpedthrough the sand.

The volumes of fluids collected in the receiver are measured and therelative amount of oil and water displaced from the rock sample aredetermined and recorded. Of special interest is the volume of oildisplaced as a fraction of the original pore volume. This informationmay be viewed as an indication of the approximate percentage of oiloriginally in place which is produced by natural water drive followingdrilling of a well into the rock formation followed by the primary phaseof field production carried to the approximate economic limit.

Following this step, one to three additional pore volumes of watercontaining TFSA micellar solution to be tested are pumped slowly throughthe plug and the volumes of additional oil and water displaced aredetermined. Typically, where such an initial "slug" of micellar TFSAsolution is introduced, it may be contained in a volume of fluid rangingfrom 1% to 100% of the pore volume, but most frequently it will be in aslug volume of 10% to 50% of pore volume.

After this final displacement step, the produced oil and water are againmeasured. By comparing the amount of oil produced by this additionalinjection of water containing, or preceded by a solution, of micellarTFSA solution with the amount produced when the same volume of watercontaining no TFSA solution is injected, one can evaluate theeffectiveness of the particular micellar TFSA solution used forenhancing the recovery of additional oil over and above that obtained byordinary waterflooding.

Generally, six or more sand columns of the kind described above aremounted in the heated air bath. Test of a given micellar TFSA solutionis then run in triplicate, using identical conditions andconcentrations, simultaneously with three blank tests run similarly butwithout addition of micellar TFSA solution to the water.

The composition of Example F was tested by this procedure with thefollowing conditions:

    ______________________________________                                        Oil          Ranger Zone, Wilmington, Calif., field                                        API Gravity approximately 13.5                                   Water        Mixed water used in flood operations                             Airbath Temperature                                                                        150° F. (Same as formation temperature)                   ______________________________________                                    

Oil was displaced by pumping two pore volumes of water into the sand.After measuring the volumes of oil and water produced through the bottomline, a further 0.2 pore volumes of water containing 2,600 ppm of thecomposition of Example F was injected followed by 2.8 volumes of watercontaining 175 ppm of the composition of Example D. Measurement of thevolumes of oil and water produced were read after each 0.2 pore volumesof water was injected.

Results of this test at the points of 2,3 and 5 pore volumes of injectedwater are given in the table below wherein averages of three duplicatedeterminations are presented.

    ______________________________________                                        Oil Recovery as % of                                                          Oil in Place                                                                                     Composition of                                                                            Ratio of Increment                                                Example F   of Oil Production                              Pore Volumes                                                                            No       Added to Water                                                                            After Initial 2                                (P.V.) of Chemical after Initial                                                                             P.V. Chemical/                                 Water Injected                                                                          Addition 2 P.V. of Water                                                                           No Chemical                                    ______________________________________                                        2         36.5     36.5        --                                             3         40.0     43.7        2.1                                            5         43.1     53.0        2.5                                            ______________________________________                                    

Use of the composition of Example F in the amounts given above resultedin the production of 110% more oil from injection of one incrementalpore volume of water than was produced by water injection alone and gave150% more oil after three incremental pore volumes of treated waterinjection.

Although the invention has been described in terms of specifiedembodiments which are set forth in detail, it should be understood thatthis is by illustration only and that the invention is not necessarilylimited thereto, since alternative embodiments and operating techniqueswill become apparent to those skilled in the art in view of thedisclosure. Accordingly, modifications are contemplated which can bemade without departing from the spirit of the described invention.

What is claimed and desired to be secured by Letters Patent is:
 1. Amethod for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a homogeneousmicellar solution of a thin film spreading agent, said micellar solutioncomprising: (1) from between about 5% and about 75% by weight of anacylated polyether polyol having the formula: ##STR6## wherein: A is analkylene oxide group, --C_(i) H_(2i) O--;O is oxygen; i is a positiveinteger from 2 to about 10; j is a positive integer no greater thanabout 100; k is a positive integer no greater than about 100; N isnitrogen; R¹ is one of hydrogen, a monovalent hydrocarbon groupcontaining less than about C₁₁, or [A_(L) H]; L is a positive integer nogreater than about 100; R is a hydrocarbon moiety of a polyol, a primaryor secondary amine, a primary or secondary polyamine, a primary orsecondary amino alcohol, or hydrogen; and m+n is no greater than about 4when R is other than hydrogen and one of m and n is zero and the otheris unity when R is hydrogen, said acylated polyether polyol being thereaction product of said polyether polyol and a member selected from theclass consisting of mono- and polybasic carboxylic acids, acidanhydrides, and iso-, diiso-, and polyisocyanates, said acylatedpolyether polyol at about 25° C.: (a) being less than about 1% by volumesoluble in water and in isooctane; (b) having a solubility parameter inthe range of between about 6.9 and about 8.5; and (c) spreading at theinterface between distilled water and refined mineral oil to form a filmhaving a thickness no greater than about 20 Angstroms at a spreadingpressure of about 16 dynes per cm; (2) from between about 2% and about30% by weight of a hydrotropic agent having one of the formulas:

    X-Z                                                        (A)

wherein X is an alkyl, alicyclic, aromatic, alkylalicyclic, alkylaryl,arylalkyl, alicyclicalkyl, heterocyclic or substituted heterocyclicradical having 2 to 13 carbon atoms; and wherein Z is one of: --OH;##STR7## and --OCH₃ ; and U and V are hydrogen or hydrocarbonsubstituents;

    --X--Y--R--(Z).sub.n,                                      (B)

wherein: Z is one of --OH; ##STR8## and --OCH₃ ; X is an alkyl,alicyclic, aromatic, alkylalicyclic, alkylaryl, arylalkyl,alicyclicalkyl, heterocyclic or substituted heterocyclic radical having2 to 12 carbon atoms; R is a member selected from the class consistingof, --CH₂ --,--C₂ H₄ --,C₃ H₅ ═,--C₃ H₆, and --C₂ H₄ --O--C₂ H₄ --; n iseither a one or two integer, the integer dependent upon the selection ofR; U and V are hydrogen or hydrocarbon substituents; and Y is a memberselected from the class consisting of: ##STR9## --O--, and --S--; (3)from between about 2% and about 30% by weight of an amphipathic agenthaving at least one radical having from between about 10 and about 64carbon atoms per molecule; and (4) from between about 15% and about 90%by weight, water.
 2. The method of claim 1 wherein said acylatedpolyether polyol is the reaction product of a difunctional polyetherpolyol and a difunctional member of the class consisting of carboxylicacids, acid anhydrides and isocyanates.
 3. The method of claim 1 whereinsaid acylated polyether polyol is the reaction product of a polyetherpolyol and an acylating agent selected from the class consisting of di-and mono-basic acids and anhydrides having C₁₃ or less.
 4. The method ofclaim 1 wherein said acylated polyether polyol is the reaction productof a polyether polyol and a polyisocyanate containing at least twoisocyanate groups.
 5. The method of claim 1 wherein the hydrotropicagent is an alcohol.
 6. The method of claim 1 wherein the hydrotropicagent is an aldehyde.
 7. The method of claim 1 wherein the hydrotropicagent is a semi-polar oxygen-containing compound capable of forminghydrogen bonds.
 8. The method of claim 1 wherein the hydrotropic agentis an amine.
 9. The method of claim 1 wherein the hydrotropic agent is acarboxy amide.
 10. The method of claim 1 wherein the amphipathic agentis a hydrophobic hydrocarbon residue-containing composition wherein thehydrocarbon residue is aliphatic, alkylalicyclic, aromatic, arylalkyl oralkylaromatic.
 11. The method of claim 1 wherein the amphipathic agentcomprises mahogany or green sulfonates of petroleum, petroleumfractions, or petroleum extracts.
 12. The method of claim 1 wherein theamphipathic agent is anionic.
 13. The method of claim 1 wherein theamphipathic agent is cationic.
 14. The method of claim 1 wherein theamphipathic agent is nonionic.
 15. A method for breaking petroleumemulsions of the water-in-oil type characterized by subjecting theemulsion to the action of a micellar solution of a thin film spreadingagent, said homogeneous micellar solution comprising: (1) from betweenabout 5% and about 75% by weight of an acylated polyether polyol whereinsaid polyether polyol has an average molecular weight of 15,000 or lessand is derived from the reaction of an alkylene oxide containing lessthan about 10 carbon atoms with a member of the group consisting ofpolyols, amines, polyamines and amino alcohols containing from about 2to about 10 active hydrogen groups capable of reaction with alkyleneoxides, said member having 18 or less carbon atoms, and the acylatingagent being a member selected from the class consisting of mono- andpolybasic carboxylic acids, acid anhydrides and iso-, diiso-, andpolyisocyanates, said acylated polyether polyol, at about 25° C.: (A)having a solubility in water and isooctane of less than about 1%, byvolume; (B) having a solubility parameter from between about 6.8 andabout 8.5; and (C) spreading at the interface between white, refinedmineral oil and distilled water to form a film having a calculatedthickness no greater than about 20 Angstroms, at a spreading pressure ofabout 16 dynes per cm; (2) from between about 2% and about 30% by weightof a hydrotropic agent comprising a semi-polar hydrogen bond formingcompound containing at least one of oxygen, nitrogen and sulfur and frombetween about 2 and about 12 carbon atoms; (3) from between about 2% andabout 20% by weight of an amphipathic agent having at least one radicalhaving from between about 10 and about 64 carbon atoms per molecule; and(4) from between about 15% and about 90% by weight, water.
 16. Themethod of claim 15 wherein the amphipathic agent is a hydrophobichydrocarbon residue-containing composition wherein the hydrocarbonresidue is aliphatic, alkylalicyclic, aromatic, arylalkyl oralkylaromatic.
 17. The method of claim 15 wherein the amphipathic agentcomprises mahogany or green sulfonates of petroleum, petroleumfractions, or petroleum extracts.
 18. The method of claim 15 wherein theamphipathic agent is anionic.
 19. The method of claim 15 wherein theamphipathic agent is cationic.
 20. The method of claim 15 wherein theamphipathic agent is nonionic.
 21. A method of recovering oil from anoil-bearing formation into which a well bore extends, comprising thesteps of: (I) generating steam at the surface; (II) supplying said steamto said oil-bearing formation by way of said well bore; (III) supplyinga homogeneous micellar solution of a thin film spreading agent to saidoil-bearing formation to inhibit the production of oil-water emulsion asa result of the interaction of said steam with the oil and water in theformation said agent comprising: (1) from between about 5% and about 75%by weight of an acylated polyether polyol having the formula: ##STR10##wherein: A is an alkylene oxide group, -C_(i) H_(2i) O-;O is oxygen; iis a positive integer from 2 to about 10; j is a positive integer nogreater than about 100; k is a positive integer no greater than about100; N is nitrogen; R¹ is one of hydrogen, a monovalent hydrocarbongroup containing less than about C₁₁, or [A_(L) H]; L is a positiveinteger no greater than about 100; R is a hydrocarbon moiety of apolyol, a primary or secondary amine, a primary or secondary polyamine,a primary or secondary amino alcohol, or hydrogen; and m+n is no greaterthan about 4 when R is other than hydrogen and one of m and n is zeroand the other is unity when R is hydrogen, said acylated polyether beingthe reaction product of said polyether polyol and a member selected fromthe class consisting of mono- and polybasic carboxylic acids, acidanhydrides, and iso-, or diiso-, and polyisocyanates, said acylatedpolyether polyol at about 25° C.: (a) being less than about 1% by volumesoluble in water and in isooctane; (b) having a solubility parameter inthe range of between about 6.9 and about 8.5; and (c) spreading at theinterface between distilled water and refined mineral oil to form a filmhaving a thickness no greater than about 20 Angstroms at a spreadingpressure of about 16 dynes per cm; (2) from between about 2% and about30% by weight of a hydrotropic agent having one of the formulas:

    X--Z                                                       (A)

wherein X is an alkyl, alicyclic, aromatic, alkylalicyclic, alkylaryl,arylalkyl, alicyclicalkyl, heterocyclic or substituted heterocyclicradical having 2 to 13 carbon atoms; and wherein Z is one of: --OH;##STR11## and --OCH₃ ; and U and V are hydrogen or hydrocarbonsubstituents;

    X--Y--R--(Z).sub.n,                                        (B)

wherein: Z is one of --OH; ##STR12## and --OCH₃ ; X is an alkyl,alicyclic, aromatic, alkylalicyclic, alkylaryl, arylalkyl,alicyclicalkyl, heterocyclic or substituted heterocyclic radical having2 to 12 carbon atoms; R is a member selected from the class consistingof, --CH₂ --, --C₂ H₄ --, C₃ H₅ ═, --C₃ H₆, and --C₂ H₄ --O--C₂ H₄ --; nis either a one or two integer, the integer dependent upon the selectionof R; U and V are hydrogen or hydrocarbon substituents; and Y is amember selected from the class consisting of: ##STR13## --O--, and--S--; (3) from between about 2% and about 30% by weight of anamphipathic agent having at least one radical having from between about10 and about 64 carbon atoms per molecule; (4) from between about 15%and about 90% by weight, water; and (IV) recovering from said formationoil and water which was subjected to the action of said steam.
 22. Themethod of claim 21, wherein said acylated polyether polyol is thereaction product of a difunctional polyether polyol and a difunctionalmember of the class consisting of carboxylic acids, acid anhydrides andisocyanates.
 23. The method of claim 21, wherein said acylated polyetherpolyol is the reaction product of a polyether polyol and an acylatingagent selected from the class consisting of di- and mono-basic acids andanhydrides having C₁₃ or less.
 24. The method of claim 21, wherein saidacylated polyether polyol is the reaction product of a polyether polyoland a polyisocyanate containing at least two isocyanate groups.
 25. Themethod of claim 21, wherein the hydrotropic agent is an alcohol.
 26. Themethod of claim 21, wherein the hydrotropic agent is an hydroxy ester ofa polyol.
 27. The method of claim 21, wherein the hydrotropic agent isan aldehyde.
 28. The method of claim 21, wherein the hydrotropic agentis a semi-polar oxygen-containing compound capable of forming hydrogenbonds.
 29. The method of claim 21, wherein the amphipathic agent is ahydrophobic hydrocarbon residue-containing composition wherein thehydrocarbon residue is aliphatic, alkylalicyclic, aromatic, arylalkyl oralkylaromatic.
 30. The method of claim 21, wherein the amphipathic agentcomprises mahogany or green sulfonates of petroleum, petroleumfractions, or petroleum extracts.
 31. The method of claim 21, whereinthe amphipathic agent is anionic.
 32. The method of claim 21, whereinthe amphipathic agent is cationic.
 33. The method of claim 21, whereinthe amphipathic agent is nonionic.
 34. A method of recovering oil froman oil-bearing formation into which a well bore extends, comprising thesteps of: (I) generating steam at the surface; (II) supplying said steamto said oil-bearing formation by way of said well bore; (III) supplyinga homogeneous micellar solution of a thin film spreading agent to saidoil-bearing formation to inhibit the production of oil-water emulsion asa result of the interaction of said steam with the oil and water in theformation, said micellar solution comprising: (1) from between about 5%and about 75% by weight of an acylated polyether polyol wherein saidpolyether polyol has an average molecular weight of 15,000 or less andis derived from the reaction of an alkylene oxide containing less thanabout 10 carbon atoms with a member of the group consisting of polyols,amines, polyamines and amino alcohols containing from about 2 to about10 active hydrogen groups capable of reaction with alkylene oxides, saidmember having 18 or less carbon atoms and the acylating agent being amember selected from the class consisting of mono- and polybasiccarboxylic acids, acid anhydrides and iso-, diiso-, and polyisocyanates,said acylated polyether polyol, at about 25° C.: (A) having a solubilityin water and isooctane of less than about 1% by volume; (B) having asolubility parameter from between about 6.8 and about 8.5; and (C)spreading at the interface between white, refined mineral oil anddistilled water to form a film having a calculated thickness no greaterthan about 20 Angstroms, at a spreading pressure of about 16 dynes percm; (2) from between about 2% and about 30% by weight of a hydrotropicagent comprising a semi-polar hydrogen bond forming compound containingat least one of oxygen, nitrogen and sulfur and from between about 2 andabout 12 carbon atoms; (3) from between about 2% and about 20% by weightof an amphipathic agent having at least one radical having from betweenabout 10 and about 64 carbon atoms per molecule; (4) from between about15% and about 90% by weight, water and (IV) recovering from saidformation oil and water which was subjected to the action of said steam.35. A method of breaking petroleum or bitumen emulsions of watercomprising contacting the emulsion with a sufficient emulsion-breakingamount of a homogeneous micellar solution of a thin film spreading agentsaid micellar solution comprising: (1) from between about 5% and about75% by weight of an acylated polyether polyol wherein said polyetherpolyol has an average molecular weight of 15,000 or less and is derivedfrom the reaction of an alkylene oxide containing less than about 10carbon atoms with a member of the group consisting of polyols, amines,polyamines and amino alcohols containing from about 2 to about 10 activehydrogen groups capable of reaction with alkylene oxides, said memberhaving 18 or less carbon atoms, and the acylating agent being a memberselected from the class consisting of mono- and polybasic carboxylicacids, said anhydrides and iso-, diiso-, and polyisocyanates, saidacylated polyether polyol, at about 25° C.: (A) having a solubility inwater and isooctane of less than about 1%, by volume; (B) having asolubility parameter from between about 6.8 and 8.5; and (C) spreadingat the interface between white, refined mineral oil and distilled waterto form a film having a calculated thickness no greater than about 20Angstroms, at a spreading pressure of about 16 dynes per cm; (2) frombetween about 2% and about 30% by weight of a hydrotropic agentcomprising a semi-polar hydrogen bond forming compound containing atleast one of oxygen, nitrogen and sulfur and from between about 2 andabout 12 carbon atoms; (3) from between about 2% and about 20% by weightof an amphipathic agent having at least one radical having from betweenabout 10 and about 64 carbon atoms per molecule; and (4) from betweenabout 15% and about 90% by weight, water.
 36. In the method ofpreventing the formation of emulsions of an aqueous phase and apetroleum oil or bitumen phase, the improvement comprising: contactingsaid petroleum oil or bitumen phase prior to or coincident with itscontact with the aqueous phase with an effective emulsion preventingamount of a homogeneous micellar solution of a thin film spreadingagent, said micellar solution comprising: (1) from between about 5% andabout 75% by weight of an acylated polyether polyol wherein saidpolyether polyol has an average molecular weight of 15,000 or less andis derived from the reaction of an alkylene oxide containing less thanabout 10 carbon atoms with a member of the group consisting of polyols,amines, polyamines and amino alcohols containing from about 2 to about10 active hydrogen groups capable of reaction with alkylene oxides, saidmember having 18 or less carbon atoms, and the acylating agent being amember selected from the class consisting of mono- and polybasiccarboxylic acids, acid anhydrides and iso-, diiso-, and polyisocyanates,said acylated polyether polyol, at about 25° C: (A) having a solubilityin water and isooctane of less than about 1% by volume; (B) having asolubility parameter of from between about 6.8 and about 8.5; and (C)spreading at the interface between white, refined mineral oil anddistilled water to form a film having a calculated thickness no greaterthan about 20 Angstroms, at a spreading pressure of about 16 dynes percm; (2) from between about 2% and about 30% by weight of a hydrotropicagent comprising a semi-polar hydrogen bond forming compound containingat least one of oxygen, nitrogen and sulfur and from between about 2 andabout 12 carbon atoms; (3) from between about 2% and about 20% by weightof an amphipathic agent having at least one radical having from betweenabout 10 and about 64 carbon atoms per molecule; and (4) from betweenabout 15% and about 90% by weight, water.
 37. In the method of breakingand preventing emulsions of water in bitumen during the recovery ofbitumen or heavy oil from tar sands and subterranean deposits bysteaming, flooding, and combinations thereof, the improvementcomprising: contacting said bitumen or heavy oil with a homogeneousmicellar solution of a thin film spreading agent, comprising: (1) frombetween about 5% and about 75% by weight of an acylated polyether polyolwherein said polyether polyol has an average molecular weight of 15,000or less and is derived from the reaction of an alkylene oxide containingless than about 10 carbon atoms with a member of the group consisting ofpolyols, amines, polyamines and amino alcohols containing from about 2to about 10 active hydrogen groups capable of reaction with alkyleneoxides, said member having 18 or less carbon atoms, and the acylatingagent being a member selected from the class consisting of mono- andpolybasic carboxylic acids, acid anhydrides and iso-, diiso-, andpolyisocyanates, said acylated polyether polyol, at about 25° C.: (A)having a solubility in water and isooctane of less than about 1%, byvolume; (B) having a solubility parameter from between about 6.8 andabout 8.5; and (C) spreading at the interface between white, refinedmineral oil and distilled water to form a film having a calculatedthickness no greater than about 20 Angstroms, at a spreading pressure ofabout 16 dynes per cm; (2) from between about 2% and about 30% by weightof a hydrotropic agent comprising a semi-polar hydrogen bond formingcompound containing at least one of oxygen, nitrogen and sulfur and frombetween about 2 and about 12 carbon atoms; (3) from between about 2% andabout 20% by weight of an amphipathic agent having at least one radicalhaving from between about 10 and about 64 carbon atoms per molecule; and(4) from between about 15% and about 90% by weight, water.
 38. Themethod of claim 34, 35, 36 or 37 wherein said acylated polyether polyolis the reaction product of a difunctional polyether polyol and adifunctional member of the class consisting of carboxylic acids, acidanhydrides and isocyanates.
 39. The method of claim 34, 35, 36 or 37wherein said acylated polyether polyol is the reaction product of apolyether polyol and a polyisocyanate containing at least two isocyanategroups.
 40. The method of claim 34, 35, 36 or 37 wherein the hydrotropicagent is an alcohol.
 41. The method of claim 34, 35, 36 or 37 whereinthe hydrotropic agent is an hydroxy ester of a polyol.
 42. The method ofclaim 34, 35, 36 or 37 wherein the hydrotropic agent is an aldehyde. 43.The method of claim 34, 35, 36 or 37 wherein the hydrotropic agent is asemi-polar oxygen-containing compound capable of forming hydrogen bonds.44. The method of claim 34, 35, 36 or 37 wherein the hydrotropic agentis an amine.
 45. The method of claim 34, 35, 36 or 37 wherein thehydrotropic agent is a carboxy amide.
 46. The method of claim 34, 35, 36or 37 wherein the hydrotropic agent is a phenolate.
 47. The method ofclaim 34, 35, 36 or 37 wherein the amphipathic agent is a hydrophobichydrocarbon residue-containing composition wherein the hydrocarbonresidue is aliphatic, alkylalicyclic, aromatic, arylalkyl oralkylaromatic.
 48. The method of claim 34, 35, 36 or 37 wherein theamphipathic agent contains an uninterrupted chain of from between about10 and about 22 carbons.
 49. The method of claim 34, 35, 36 or 37wherein the amphipathic agent is an anion-active soap.
 50. The method ofclaim 34, 35, 36 or 37 wherein the amphipathic agent comprises mahoganyor green sulfonates of petroleum, petroleum fractions, or petroleumextracts.
 51. The method of claim 34, 35, 36 or 37 wherein theamphipathic agent is anionic.
 52. The method of claim 34, 35, 36 or 37wherein the amphipathic agent is cationic.
 53. The method of claim 34,35, 36 or 37 wherein the amphipathic agent is nonionic.